US6096930A - Herbicidal cyclohexane-1,3-dione derivatives and their preparation process - Google Patents

Herbicidal cyclohexane-1,3-dione derivatives and their preparation process Download PDF

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US6096930A
US6096930A US09/075,787 US7578798A US6096930A US 6096930 A US6096930 A US 6096930A US 7578798 A US7578798 A US 7578798A US 6096930 A US6096930 A US 6096930A
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Eung Kul Ryu
Kyoung Mahn Kim
Jae Nyoung Kim
Jin Seog Kim
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Korea Research Institute of Chemical Technology KRICT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/42—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/52—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/54—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

Definitions

  • the present invention relates to novel cyclohexane-1,3-dione derivatives of the following formula (1) useful as herbicides and plant-growth regulants. ##STR2## wherein,
  • X is selected from the group consisting of hydrogen, halogen, C 1 ⁇ C 6 alkyl, C 2 ⁇ C 6 alkoxy, C 1 ⁇ C 6 haloalkyl, nitro, C 1 ⁇ C 6 alkylthio, C 1 ⁇ C 6 alkylsulfinyl, C 1 ⁇ C 6 alkylsulfonyl, C 1 ⁇ C 6 sulfamoyl, and N, N-di(C 1 ⁇ C 6 alkyl)sulfamoyl group;
  • (X)n represents the number of X substituents which may be substituted on benzene ring, wherein n is 1, 2 or 3. Also, cyclohexyl moiety, one of the substituents on benzofuran ring, is substituted at C-4, C-5, C-6 or C-7 position on benzen ring;
  • R 1 is selected from the group consisting of hydrogen and C 1 ⁇ C 6 alkyl group
  • R 2 is selected from the group consisting of C 1 ⁇ C 6 alkyl, C 2 ⁇ C 6 alkenyl and C 2 ⁇ C 6 alkynyl group;
  • R 3 is selected from the group consisting of hydrogen, C 1 ⁇ C 6 alkyl, C 1 ⁇ C 6 haloalkyl, C 2 ⁇ C 6 alkenyl, C 2 ⁇ C 6 haloalkenyl, C 2 ⁇ C 6 alkoxyalkyl, C 2 ⁇ C 6 alkylthioalkyl, benzyl and C 2 ⁇ C 6 haloalkanoyl group;
  • R 4 is selected from the group consisting of hydrogen, alkali metal cation, alkaline earth metal cation, C 1 ⁇ C 4 alkanoyl, C 1 ⁇ C 4 haloalkanoyl and benzoyl group.
  • Cyclohexane-1,3-dione derivatives and their herbicidal activity were already known in the arts.
  • Alloxidim-sodium Australian Patent No. 464,655; British Patent No. 1,461,170; U.S. Pat. No. 3,950,420
  • Sethoxydim German Patent No. 2,822,304
  • cyclohexane-1,3-dione derivatives having substituted phenyl group U.S. Pat. No. 4,639,267 and U.S. Pat. No. 4,652,303
  • But cyclohexane-1,3-dione derivatives having 2,3-dihydroindanyl group such as the above formula(1) compound of the present invention have not been known.
  • the object of the present invention is to provide novel compounds of the above formular (1) and its preparation processes.
  • Another object is to provide herbicidal composition with strong herbicidal activity and good selectivity, especially for paddy rice and broad leaved plant, containing a compound of formula (1) as active ingredient.
  • the present invention is identified as cyclohexane-1,3-dione derivatives of the following formula (1). ##STR3## wherein, (X)n, R 1 , R 2 , R 3 and R 4 are respectively defined as described above.
  • X is selected from the group consisting of hydrogen, halogen and C 1 ⁇ C 6 alkyl group; n is 1, 2 or 3; R 1 is selected from the group consisting of hydrogen and C 1 ⁇ C 6 alkyl group; R 2 is selected from the group consisting of C 1 ⁇ C 6 alkyl group; R 3 is selected from the group consisting of hydrogen, C 1 ⁇ C 6 alkyl, C 2 ⁇ C 6 alkenyl and C 2 ⁇ C 6 haloalkenyl group; R 4 is hydrogen.
  • Typical compounds of the above formula (1) according to the present invention are as follows:
  • the formula is intended to cover all tautomers, the present invention encompasses within its scope all the tautomers and their mixtures of compound of the formula (1).
  • reaction Scheme A A processes for the preparation of compounds (1) is shown in reaction Scheme A. ##STR6## wherein, (X)n, R 1 , R 2 , R 3 and R 4 are respectively defined as described above; Y is selected from the group consisting of halogen and --O--CO--R 2 group; Z is selected from the group consisting of halogen and hydroxy group.
  • cyclohexane-1,3-dione derivatives of the above formula (2) are reacted with acid halide or acid anhydride in an inert organic solvent to obtain the cyclohexanone ester of the above formula (3).
  • the compound (3) is rearranged in the presence of catalyst such as pyridine, 4-(dimethylamino)pyridine or 1,8-diazabicylo[5.4.0]undec-7-ene, etc. and an inert organic solvent such as benzene, toluene or xylene, etc. to obtain 2-acyl-1,3-cyclohexandione derivatives of the above formula (4).
  • catalyst such as pyridine, 4-(dimethylamino)pyridine or 1,8-diazabicylo[5.4.0]undec-7-ene, etc.
  • an inert organic solvent such as benzene, toluene or xylene, etc.
  • benzalacetone derivatives of the above formula (5) are reacted with malonic ester in the presence of alkoxide containg alkali metal or alkalin earth metal in anhydrous alcohol solvent at the boiling temperature of alcohol solvent to obtain cyclohexan-1,3-dione-4-carboxylic acid of the above formula (6).
  • the compound (6) is decarboxylated using strong acid such as hydrochloric acid or sulfuric acid, etc. to obtain the compound of the above formula (2).
  • substituted benzaldehyde derivatives of the formula (7) are reacted with acetone in the presence of base catalyst such as alkali metal hydroxide or alkalin earth metal hydroxide in water or a mixture of water and alcohol to obtain the compound of the above formula (5).
  • base catalyst such as alkali metal hydroxide or alkalin earth metal hydroxide in water or a mixture of water and alcohol
  • benzene derivatives of the formula (8) are reacted with malonyl halide in the presence of Lewis acid such as AlCl 3 , FeCl 3 , TiCl 4 or BF 3 .OEt 2 , etc., called Fiedel-Craft acylation, to obtain 2-methyl-2-alkylindan-1,3-dione derivatives of the above formula (9).
  • Aforesaid preparation processes consistute the major object of the present invention.
  • Novel compounds of the above formula (1) which are divided into formula (1-a), (1-b) and (1-c), are typically listed in following Table 1 ⁇ 3 respectively.
  • Novel cyclohexane-1,3-dione derivatives of the formula(1) according to the present invention are sufficiently tolerant on most broad leaved plant such as soybeans, cotton, sunflower, sugarbeet and various kings of vegetables and may be available for post-emergent control of grassy weeds in said crops.
  • the compounds of formula(1) according to the present invention may be applied for instance in form of wettable powders, dust, flowable concentrates, granules, solutions or emulsifiable concentrates.
  • the content of the compound of the formula(1) is usually from 0.1 to 95% by weight for these formulations in order to get sufficient effects as herbicides and plant-growth regulants.
  • solid carrier inorganic powders such as kaolinite, bentonite, montmorillonite, talc diatomaceous earth, mica, gypsum, calcium carbonate, apatite, synthesized silicon hydroxide hydrate; plant powders such as soy powder, wheat powder, sawdust, tabacco powder, starch powder, crystallized cellulose; polymers such as petroleum resin, vinyl chloride resin, ketone resin; alumina or beeswax etc. can be used.
  • inorganic powders such as kaolinite, bentonite, montmorillonite, talc diatomaceous earth, mica, gypsum, calcium carbonate, apatite, synthesized silicon hydroxide hydrate
  • plant powders such as soy powder, wheat powder, sawdust, tabacco powder, starch powder, crystallized cellulose
  • polymers such as petroleum resin, vinyl chloride resin, ketone resin; alumina or beeswax etc.
  • alcohols such as methanol, ethanol, ethylene glycol, benzyl alcohol; aromatic hydrocarbons such as toluene, benzene, xylene, methyl naphthalene, halohydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene; ethers such as dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyleneglycol acetate; amides such as dimethyl formamide; nitriles such as acetonitrile; ether alcohols such as ethylene glycol, diethyl ethers or water etc. can be used.
  • aromatic hydrocarbons such as toluene, benzene, xylene, methyl naphthalene, halohydrocarbons such as chloroform, carbon
  • Surfactants can be advantageously employed herein such as various cationic, anionic and nonionic surfactants.
  • Cationic surfactants include long chain alkylammonium salts such as cetyltrimethylammonium bromide, etc.
  • Anionic surfactants include alkali metal, alkaline earth metal and ammonium salts of alkylarylsulfonic acids such as dodecylbenzenesulfonic acid; alkylsulfonic acids; alkylsulfuric acids such as laurylsulfuric acid; ligninsulfonic acid; arylsulfonic acids such as naphthalenesulfonic acid or dibutylnaphthalenesulfonic acid; lauryl ether sulfate; fatty alcohol sulfates; fatty acids; salts of sulfated hexadecanols, heptadecanols or octadecanois; salts of sulfated fatty alcohol glycol ethers, etc.
  • alkylarylsulfonic acids such as dodecylbenzenesulfonic acid
  • alkylsulfonic acids alkylsulfuric acids such as laurylsul
  • nonionic surfactants include condensation products of fatty alcohols such as oleyl alcohol or cetyl alcohol; phenols; alkylphenols or caster oil with ethylene oxide or propylene oxide; condensation products of naphthalene or naphthalene sulfonic acids with phenol or formaldehyde, etc.
  • the application amount of compound represented by the formula(1) is from 0.06 kg to 8 kg/ha, preferably from 0.25 kg to 1 kg/ha.
  • the active herbicidal compounds of this invention may be formulated with insecticides, fungicides, nematocides, plant growth regulators, fertilizers, other herbicides or other agricultural chemicals.
  • the herbicidal activity test is proceeded according to the following methods.
  • the sterilized sandy loam soil is filled in test pot having a surface area of 348 cm 2 for upland test conditions or 115 cm 2 for paddy test species were planted in furrows.
  • the concentration of the test compound in solution was varied to give a range of application rates, generally 4.0 kg/ha and submultiples thereof.
  • the pots were placed in a greenhouse and watered regularly at the soil surface for 21 days and herbicidal effects were visually rated by a percent control.
  • the pots for the post-emergent tests were placed in a greenhouse and watered for 9 ⁇ 14 days, then the foliage of test plants was sprayed with a solution of the test compound in a mixture of acetone and water containing a small amount of Tween 20.
  • the herbicidal activity data were taken visually by percent control, wherein 0 signifies no herbicidal effect and 100 signifies complete kill.
  • the compounds of formula (I) of the present invention are used as herbicides or plant growth regulants, for example, the above compounds are suitable for selective elimination of weeds when useful plant is cultivated. Also, the compounds of formula (I) have the effect of growth inhibition and growth regulation for useful plant, for example, cereals, soybean, wheat or rice.
  • the compounds of formula (I) as prominent herbicides may be applied directly to soil for pre-emergence treatment and to the plant for post-emergence treatment.
  • the compounds of formula (I) of the present invention generally have more prominent herbicidal activity when are treated to leaves for post-emergence, and have strong safety for the broad-leaved plant, for example, soybean, cotton, sulflower, sugarbeet or vegetables. And these compounds have selectively herbicidal activity against grasses, and may be useful as herbicides in broad-leaved crops.
  • Certain of formula (I) compounds of the present invention especialy have prominent selectivity within the group of grasses and may be used at rate sufficient to control grass weeds in cultivated crops, for example, rice, wheat or barley, and have selectively herbicidal activity against wild grasses such as wildoat or barnyardgrass.

Abstract

The present invention relates to novel cyclohexane-1-3-dione derivatives of formula (1) useful as herbicides and plant-growth regulants, ##STR1## wherein X is selected from the group consisting of hydrogen, halogen, C1 -C6 alkyl, C2 -C6 alkoxy, C1 -C6 haloalkyl, nitro, C1 -C6 alkylthio, C1 -C6 alkylsulfinyl, C1 -C6 alkylsulfonyl, C1 -C6 sulfamoyl, and N, N-di(C1 -C6 alkyl)sulfamoyl group; (X)n represents the number of X substituents which may be substituted on benzene ring, wherein n is 1, 2 or 3. Also, cyclohexyl moiety, one of the substituents on benzofuran ring, is substituted at C-4, C-5, C-6 or C-7 position on benzene ring; R1 is selected from the group consisting of hydrogen and C1 -C6 alkyl group; R2 is selected from the group consisting of C1 -C6 alkyl, C2 -C6 alkenyl and C2 -C6 alkynyl group; R3 is selected from the group consisting of hydrogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C2 -C6 alkenyl, C2 -C6 haloalkenyl, C2 -C6 alkoxyalkyl, C2 -C6 alkylthioalkyl, benzyl and C2 -C6 haloalkanoyl group; R4 is selected from the group consisting of hydrogen, alkali metal cation, alkaline earth metal cation, C1 -C4 alkanoyl, C1 -C4 haloalkanoyl and benzoyl group.

Description

This is a division of application Ser. No. 08/793,042 filed Jun. 18, 1997, now abandoned, which is a National Stage Application under 35 U.S.C. § 371 of International Application PCT/KR95/00092, all of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates to novel cyclohexane-1,3-dione derivatives of the following formula (1) useful as herbicides and plant-growth regulants. ##STR2## wherein,
X is selected from the group consisting of hydrogen, halogen, C1 ˜C6 alkyl, C2 ˜C6 alkoxy, C1 ˜C6 haloalkyl, nitro, C1 ˜C6 alkylthio, C1 ˜C6 alkylsulfinyl, C1 ˜C6 alkylsulfonyl, C1 ˜C6 sulfamoyl, and N, N-di(C1 ˜C6 alkyl)sulfamoyl group;
(X)n represents the number of X substituents which may be substituted on benzene ring, wherein n is 1, 2 or 3. Also, cyclohexyl moiety, one of the substituents on benzofuran ring, is substituted at C-4, C-5, C-6 or C-7 position on benzen ring;
R1 is selected from the group consisting of hydrogen and C1 ˜C6 alkyl group;
R2 is selected from the group consisting of C1 ˜C6 alkyl, C2 ˜C6 alkenyl and C2 ˜C6 alkynyl group;
R3 is selected from the group consisting of hydrogen, C1 ˜C6 alkyl, C1 ˜C6 haloalkyl, C2 ˜C6 alkenyl, C2 ˜C6 haloalkenyl, C2 ˜C6 alkoxyalkyl, C2 ˜C6 alkylthioalkyl, benzyl and C2 ˜C6 haloalkanoyl group;
R4 is selected from the group consisting of hydrogen, alkali metal cation, alkaline earth metal cation, C1 ˜C4 alkanoyl, C1 ˜C4 haloalkanoyl and benzoyl group.
DESCRIPTION OF THE RELATED ART
Cyclohexane-1,3-dione derivatives and their herbicidal activity were already known in the arts. For example, Alloxidim-sodium (Australian Patent No. 464,655; British Patent No. 1,461,170; U.S. Pat. No. 3,950,420) and Sethoxydim (German Patent No. 2,822,304) have been commercially used as herbicides. Also cyclohexane-1,3-dione derivatives having substituted phenyl group (U.S. Pat. No. 4,639,267 and U.S. Pat. No. 4,652,303) have been known. But cyclohexane-1,3-dione derivatives having 2,3-dihydroindanyl group such as the above formula(1) compound of the present invention have not been known.
Therefore, the present inventors have made efforts to develop new herbicidal compounds which have powerful herbicidal activity and good selectivity, especially useful for selective control barnyardgrass species in upland and paddy rice.
SUMMARY OF THE INVENTION
The object of the present invention is to provide novel compounds of the above formular (1) and its preparation processes.
Another object is to provide herbicidal composition with strong herbicidal activity and good selectivity, especially for paddy rice and broad leaved plant, containing a compound of formula (1) as active ingredient.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is identified as cyclohexane-1,3-dione derivatives of the following formula (1). ##STR3## wherein, (X)n, R1, R2, R3 and R4 are respectively defined as described above.
In the formula (1) according to the present invention the preferred compounds are as follows: X is selected from the group consisting of hydrogen, halogen and C1 ˜C6 alkyl group; n is 1, 2 or 3; R1 is selected from the group consisting of hydrogen and C1 ˜C6 alkyl group; R2 is selected from the group consisting of C1 ˜C6 alkyl group; R3 is selected from the group consisting of hydrogen, C1 ˜C6 alkyl, C2 ˜C6 alkenyl and C2 ˜C6 haloalkenyl group; R4 is hydrogen.
Among the compounds of the present invention, the compounds of the following formula (1-a), (1-b) and (1-c) are especially preferred. ##STR4## wherein R1, R2 and R3 are respectively defined as described above.
Typical compounds of the above formula (1) according to the present invention are as follows:
5-(2,2,4,6,7-Pentamethylindan-5-yl)-2-[1-(allyloxyimino)propyl]-3-hydroxycyclohex-2-en-1-one;
5-(2-Ethyl-2,4,5,7-tetramethylindan-6-yl)-2-[1-(allyloxyimino)propyl]-3-hydroxycyclohex-2-en-1-one;
5-(6-Chloro-2,2,4,7-tetramethylindan-5-yl)-2-[1-(ethoxyimino)butyl]-3-hydroxycyclohex-2-en-1-one;
5-(6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-2-[1-(ethoxyimino)propyl]-3-hydroxycyclohex-2-en-1-one;
5-(7-Chloro-2,2,4,5-tetramethylindan-6-yl)-2-[1-(ethoxyimino)butyl]-3-hydroxycyclohex-2-en-1-one;
5-(7-Chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-2-[1-(ethoxyimino)propyl]-3-hydroxycyclohex-2-en-1-one;
Where the compounds of the formula (1) can exhibit tautomerism, the formula is intended to cover all tautomers, the present invention encompasses within its scope all the tautomers and their mixtures of compound of the formula (1).
The compounds of the formula (1) of which R4 is hydrogen may exist in any one of four tautomeric forms as shown below. ##STR5## wherein, (X)n, R1, R2 and R3 are respectively defined as described above.
Processes for preparing the compounds (1) and their intermediates according to the present invention are as shown in reaction Scheme A˜D.
A processes for the preparation of compounds (1) is shown in reaction Scheme A. ##STR6## wherein, (X)n, R1, R2, R3 and R4 are respectively defined as described above; Y is selected from the group consisting of halogen and --O--CO--R2 group; Z is selected from the group consisting of halogen and hydroxy group.
According to the Scheme A, cyclohexane-1,3-dione derivatives of the above formula (2) are reacted with acid halide or acid anhydride in an inert organic solvent to obtain the cyclohexanone ester of the above formula (3).
The compound (3) is rearranged in the presence of catalyst such as pyridine, 4-(dimethylamino)pyridine or 1,8-diazabicylo[5.4.0]undec-7-ene, etc. and an inert organic solvent such as benzene, toluene or xylene, etc. to obtain 2-acyl-1,3-cyclohexandione derivatives of the above formula (4).
The compound (4) is reacted with substituted hydroxylamine hydrochloride (R3 ONH2.HCl) in a base catalyst such as carbonate, acetate or hydroxide containing alkai metal or alkalin earth metal, and an alcohol solvent to obtain the compound of the above formula (1, R4 =hydrogen) according to the present invention.
To obtain the compound of the above formula (1, R4 ≠hydrogen), the compound (1, R4 =hydrogen) is reacted with alkali metal hydroxide, alkalin earth metal hydroxide, acyl halide, haloacyl halide or benzoyl halide, etc.
Also, the compounds of the above formula (2) and (4) are novel compounds.
And a process for preparing the novel cyclohexane-1, 3-dione derivatives of the above formula (2) is as follows: ##STR7## wherein, (X)n and R1 are respectively defined as described above; R is selected from the group of consisting of C1 ˜C4 alkyl group; M is selected from the group of consisting of alkali metal and alkalin earth metal.
According to the Scheme B, benzalacetone derivatives of the above formula (5) are reacted with malonic ester in the presence of alkoxide containg alkali metal or alkalin earth metal in anhydrous alcohol solvent at the boiling temperature of alcohol solvent to obtain cyclohexan-1,3-dione-4-carboxylic acid of the above formula (6). The compound (6) is decarboxylated using strong acid such as hydrochloric acid or sulfuric acid, etc. to obtain the compound of the above formula (2).
And a process for preparing the above formula (5) is as follows: ##STR8## wherein, (X)n and R1 are respectively defined as described above.
According to the Scheme C, substituted benzaldehyde derivatives of the formula (7) are reacted with acetone in the presence of base catalyst such as alkali metal hydroxide or alkalin earth metal hydroxide in water or a mixture of water and alcohol to obtain the compound of the above formula (5).
And a process for preparing the above formula (7) is as follows: ##STR9## wherein, (X)n and R1 are respectively defined as described above.
According to the scheme D, benzene derivatives of the formula (8) are reacted with malonyl halide in the presence of Lewis acid such as AlCl3, FeCl3, TiCl4 or BF3.OEt2, etc., called Fiedel-Craft acylation, to obtain 2-methyl-2-alkylindan-1,3-dione derivatives of the above formula (9).
And the compound (9) is reducted by hydrochloric acid in zinc-mercury alloy (Zn/Hg) to obtain 2-methyl-2-alkylindane derivatives of the above formula (10).
And the compound (10) is reacted with α,α-dichloromethylmethylether in the presence of Lewis acid to obtaind the above formula (7). The process of introducing aldehyde group into the compound of formula (10) was disclosed in Organic Synthesis, Coll. Vol. V. 49.
Aforesaid preparation processes consistute the major object of the present invention.
Novel compounds of the above formula (1), which are divided into formula (1-a), (1-b) and (1-c), are typically listed in following Table 1˜3 respectively.
                                  TABLE 1                                 
__________________________________________________________________________
                                        (1-a)                             
                                          #STR10##                        
   -                                                                      
Compound                                                                  
  No. R.sup.1 R.sup.2 R.sup.3 mp (° C.) .sup.1 H NMR (ppm)         
__________________________________________________________________________
 1    CH.sub.3                                                            
         C.sub.2 H.sub.5                                                  
             CH.sub.3      1.13(t, 3H), 1.18(s, 6H), 2.10(s,              
       3H), 2.30(s, 6H), 2.50˜3.40(m,                               
       11H), 3.90(s, 3H), 10.8(br, 1H).                                   
   2 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5  1.10˜1.52(m, 6H),    
                           1.18(s, 6H), 2.10                              
       (s, 3H), 2.30(s, 6H), 2.50˜3.40(m,                           
       11H), 4.0(q, 2H), 10.8(br, 1H).                                    
   3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 ═CHCH.sub.2  1.20(t, 3H),      
                           1.21(s, 6H), 2.17(s,                           
       3H), 2.25(s, 3H), 2.75(s, 3H),                                     
       2.50˜3.40(m, 10H), 3.80˜4.0(m,                         
       1H), 4.6(d, 2H), 5.5(dd, 2H),                                      
       5.8˜6.2(m, 1H), 10.8(br, 1H).                                
   4 CH.sub.3 C.sub.2 H.sub.5 ClCH═CHCH.sub.2  1.20(t, 3H), 1.20(s,   
                           6H), 2.17(s,                                   
       3H), 2.25(s, 3H), 2.75(s, 3H),                                     
       2.50˜3.40(m, 11H), 3.5(d, 1H), 3.8                           
       (d, 1H), 6.2(m, 2H), 10.8(br, 1H).                                 
   5 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 ═C(CH.sub.3)CH.sub.2  1.20(t,  
                           3H), 1.21(s, 6H), 1.52(d,                      
       3H), 2.17(s, 3H), 2.40(s, 6H),                                     
       2.50˜3.40(m, 11H), 4.6(m, 2H),                               
       5.1˜5.8(m, 2H), 10.8(br, 1H).                                
   6 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.3  0.95˜1.50(m, 5H), 1.21(s, 
                           6H), 2.10                                      
       (s, 3H), 2.30(s, 6H), 2.50˜3.40(m,                           
       11H), 3.90(s, 3H), 10.8(br, 1H).                                   
   7 CH.sub.3 n-C.sub.3 H.sub.7 C.sub.2 H.sub.5  0.98˜1.62(m, 7H),  
                           1.23(s, 6H), 2.10                              
       (s, 3H), 2.30(s, 6H), 2.50˜3.40(m,                           
       11H), 4.2(q, 2H), 10.8(br, 1H).                                    
   8 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.2 ═CHCH.sub.2  0.96˜1.82(
                           m, 5H), 1.21(s, 6H), 2.17                      
       (s, 3H), 2.25(s, 3H), 2.75(s, 3H),                                 
       2.50˜3.40(m, 10H), 3.80˜4.0(m,                         
       1H), 4.6(d, 2H), 5.5(dd, 2H),                                      
       5.8˜6.2(m, 1H), 10.8(br, 1H).                                
   9 CH.sub.3 n-C.sub.3 H.sub.7 ClCH═CHCH.sub.2  0.98˜1.82(m,   
                           5H), 1.20(s, 6H), 2.17                         
       (s, 3H), 2.25(s, 3H), 2.75(s, 3H),                                 
       2.50˜3.40(m, 11H), 3.5(d, 1H), 3.8                           
       (d, 1H), 6.2(m, 2H), 10.8(br, 1H).                                 
  10 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.2 ═C(CH.sub.3)CH.sub.2         
                           0.98˜1.82(m, 5H), 1.21(s, 6H),           
       1.52(d, 3H), 2.17(s, 3H), 2.40(s,                                  
       6H), 2.50˜3.40(m, 11H), 4.6(m,                               
       2H), 5.1˜5.8(m, 2H), 10.8(br,                                
       1H).                                                               
  11 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 Oil 0.90(t, 3H), 1.10(s,    
                           3H), 1.18(t,                                   
       3H), 1.21(t, 3H), 1.52(q, 2H),                                     
       2.17(s, 3H), 2.30(s, 6H), 2.52˜                              
       3.47(m, 11H), 3.90(s, 3H), 11.2                                    
       (br, 1H).                                                          
  12 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 57˜59 0.90(t,  
                           3H), 1.10(s, 3H), 1.18(t,                      
       3H), 1.52(q, 2H), 2.17(s, 3H), 2.30                                
       (s, 6H), 2.52˜3.47(m, 11H), 4.20(q,                          
       2H), 11.2(br, 1H).                                                 
  13 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 ═CHCH.sub.2 64˜65 
                           0.90(t, 3H), 1.10(s, 3H), 1.18(t, 3H),         
                                 1.52(q, 2H), 2.17(s, 3H), 2.25(s,        
                                 3H), 2.30(s, 3H), 2.52˜2.50(m,     
                           6H),                                           
       3.05˜3.47(m, 4H), 3.80˜4.05(m,                         
       1H), 4.5(d, 2H), 5.15˜5.50(m, 2H),                           
       5.6˜6.2(m, 1H), 11.2(br, 1H).                                
  14 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ClCH═CHCH.sub.2 63˜66      
                           0.90(t, 3H), 1.10(s, 3H), 1.18(t,              
       3H), 1.52(q, 2H), 2.17(s, 3H), 2.25                                
       (s, 3H), 2.30(s, 3H), 2.62˜3.75(m,                           
       11H), 4.6(d, 1H), 4.8(d, 1H),                                      
       5.95˜6.50(m, 2H), 11.2(br, 1H).                              
  15 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 ═C(Cl)CH.sub.2 89˜
                           91 0.90(t, 3H), 1.10(s, 3H), 1.18(t,           
       3H), 1.52(q, 2H), 2.17(s, 3H),                                     
       2.25(s, 3H), 2.30(s, 3H), 2.62˜                              
       3.75(m, 11H), 4.65(s, 2H),                                         
       5.50(m, 2H), 11.2(br, 1H).                                         
  16 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.3 Oil 0.90(t, 3H), 1.10(s,  
                           3H), 1.18(t,                                   
       3H), 1.21(t, 3H), 1.52(q, 2H),                                     
       1.82(q, 2H), 2.17(s, 3H),                                          
       2.30(s, 6H), 2.52˜3.47(m, 11H),                              
       3.90(s, 3H), 11.2(br, 1H).                                         
  17 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 Oil 0.90(t, 3H),   
                           1.10(s, 3H), 1.18(t,                           
       3H), 1.21(t, 3H), 1.52(q, 2H),                                     
       1.82(q, 2H), 2.17(s, 3H),                                          
       2.30(s, 6H), 2.52˜3.47(m, 11H),                              
       4.20(q, 2H), 11.2(br, 1H).                                         
  18 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.2 ═CHCH.sub.2 Oil       
                           0.90(t, 3H), 1.10(s, 3H), 1.18(t,              
       3H), 1.21(t, 3H), 1.52(q, 2H),                                     
       1.82(q, 2H), 2.17(s, 3H),                                          
       2.25(s, 3H), 2.30(s, 3H), 2.52˜                              
       2.50(m, 6H), 3.05˜3.47(m, 4H),                               
       3.80˜4.05(m, 1H), 4.5(d, 2H),                                
       5.15˜5.50(m, 2H), 5.6˜6.2(m,                           
       1H), 11.2(br, 1H).                                                 
  19 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 ClCH═CHCH.sub.2  0.90(t, 3H),  
                           1.10(s, 3H), 1.18(t,                           
       3H), 1.21(t, 3H), 1.52(q, 2H),                                     
       1.82(q, 2H), 2.17(s, 3H),                                          
       2.25(s, 3H), 2.30(s, 3H), 2.62˜                              
       3.75(m, 11H), 4.6(d, 1H), 4.8(d,                                   
       1H), 5.95˜6.50(m, 2H), 11.2(br,                              
       1H).                                                               
  20 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.2 ═C(Cl)CH.sub.2        
                           0.90(t, 3H), 1.10(s, 3H), 1.18(t,              
       3H), 1.21(t, 3H), 1.52(q, 2H),                                     
       1.82(q, 2H), 2.17(s, 3H),                                          
       2.25(s, 3H), 2.30(s, 3H), 2.62˜                              
       3.75(m, 11H), 4.65(s, 2H),                                         
       5.50(m, 2H), 11.2(br, 1H).                                         
__________________________________________________________________________

                                  TABLE 2                                 
__________________________________________________________________________
                                        (1-b)                             
                                          #STR11##                        
   -                                                                      
Compound                                                                  
  No. R.sup.1 R.sup.2 R.sup.3 mp (° C.) .sup.1 H NMR (ppm)         
__________________________________________________________________________
21    CH.sub.3                                                            
         C.sub.2 H.sub.5                                                  
             CH.sub.3 Oil  1.15(s, 6H), 1.16(t, 3H), 2.2(s, 6H),          
       2.45˜2.9(m, 9H), 3.1(q, 2H), 3.92(s,                         
       3H), 10.5(br, 1H).                                                 
  22 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Oil 1.0(t, 3H), 1.15(s,     
                           6H), 1.32(t,                                   
       3H), 2.2(s, 6H), 2.50˜3.45(m,                                
       10H), 3.80(s, 1H), 4.0(q, 2H),                                     
       11.2(br, 1H).                                                      
  23 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 ═CHCH.sub.2 Oil 1.15(s, 6H),   
                           1.16(t, 3H), 2.2(s,                            
       6H), 2.45˜2.9(m, 9H), 4.60(dd,                               
       2H), 5.1˜5.6(m, 3H), 10.5(br,                                
       1H).                                                               
  24 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 ═C(CH.sub.3)CH.sub.2 Oil       
                           1.15(s, 6H), 1.16(t, 3H), 1.56(d,              
       3H), 2.2(s, 6H), 2.45˜2.9(m,                                 
       9H), 4.60(dd, 2H), 5.1˜5.6(m,                                
       2H), 10.5(br, 1H).                                                 
  25 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.3 Oil 0.97(t, 3H), 1.15(s, 6H),    
                           1.65(q,                                        
       2H), 2.2(s, 6H), 2.45˜2.9(m,                                 
       9H), 3.1(q, 2H), 3.92(s, 3H),                                      
       10.5(br, 1H).                                                      
  26 CH.sub.3 n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 Oil 1.0(t, 3H), 1.15(s,   
                           6H), 1.32(t, 3H),                              
       1.68(q, 2H), 2.2(s, 6H), 2.50˜3.45                           
       (m, 10H), 3.80(s, 1H), 4.0(q, 2H),                                 
       10.8(br, 1H).                                                      
  27 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.2 ═CHCH.sub.2 Oil 0.97(t, 3H), 
                           1.15(s, 6H), 1.65(q,                           
       2H), 2.2(s, 6H), 2.45˜2.9(m, 9H),                            
       4.60(dd, 2H), 5.1˜5.6(m, 3H), 10.5                           
       (br, 1H).                                                          
  28 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.2 ═C(CH.sub.3)CH.sub.2 Oil     
                           0.97(t, 3H), 1.15(s, 6H), 1.65(q,              
       2H), 2.2(s, 6H), 2.45˜2.9(m, 9H),                            
       4.60(dd, 2H), 5.1˜5.6(m, 2H), 10.5                           
       (br, 1H).                                                          
  29 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 47˜48 0.9(t, 3H),     
                           1.07(s, 3H), 1.16(t, 3H),                      
       1.50(q, 2H), 2.2(s, 6H), 2.45˜2.9(m,                         
       11H), 3.1(q, 2H), 3.92(s, 3H), 10.5                                
       (br, 1H).                                                          
  30 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Oil 0.9(t, 3H),      
                           1.05(s, 3H), 1.12(t, 3H),                      
       1.15(t, 3H), 1.5(q, 2H), 2.2(s, 6H),                               
       2.40˜2.85(m, 11H), 3.5˜4.0(m, 1H),                     
       4.15(q, 2H), 5.30(s, 1H), 9.5(br,                                  
       1H).                                                               
  31 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 ═CHCH.sub.2 41˜43 
                           0.9(t, 3H), 1.07(s, 3H), 1.16(t, 3H),          
       1.50(q, 2H), 2.2(s, 6H), 2.45˜2.9(m,                         
       11H), 3.1(q, 2H), 4.55(dd, 2H),                                    
       5.1˜5.25(m, 2H), 10.5(br, 1H).                               
  32 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ClCH═CHCH.sub.2 40˜42      
                           0.9(t, 3H), 1.07(s, 3H), 1.16(t, 3H),          
       1.50(q, 2H), 2.2(s, 6H), 2.45˜2.9(m,                         
       11H), 3.1(q, 2H), 4.55(m, 2H),                                     
       5.1˜5.25(m, 2H), 10.5(br, 1H).                               
  33 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.3 Oil 0.9(t, 3H), 1.00(s,   
                           3H), 1.10(s, 3H),                              
       1.16(t, 3H), 1.50(q, 2H), 1.70(q,                                  
       2H), 2.2(s, 6H), 2.45˜2.9(m, 11H),                           
       3.1(q, 2H), 3.92(s, 3H), 10.5(br,                                  
       1H).                                                               
  34 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 39˜41 1.0(t, 
                           3H), 1.15(s, 6H), 1.32(t, 3H),                 
       1.68(q, 2H), 2.2(s, 6H), 2.50˜3.45                           
       (m, 10H), 3.80(s, 1H), 4.0(q, 2H),                                 
       10.8(br, 1H).                                                      
  35 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.2 ═CHCH.sub.2 Oil       
                           0.9(t, 3H), 1.00(s, 3H), 1.10(s, 3H),          
       1.16(t, 3H), 1.50(q, 2H), 1.70(q,                                  
       2H), 2.2(s, 6H), 2.45˜2.9(m, 11H),                           
       3.1(q, 2H), 4.55(dd, 2H), 5.1˜5.25                           
       (m, 3H), 10.5(br, 1H).                                             
  36 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 ClCH═CHCH.sub.2 Oil 0.9(t,     
                           3H), 1.00(s, 3H), 1.10(s,                      
       3H), 1.16(t, 3H), 1.50(q, 2H),                                     
       1.70(q, 2H), 2.2(s, 6H), 2.45˜                               
       2.9(m, 11H), 3.1(q, 2H),                                           
       4.55(dd, 2H), 5.1˜5.25(m, 2H),                               
       10.5(br, 1H).                                                      
  37 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.2 ═C(Cl)CH.sub.2        
                           42˜43 0.9(t, 3H), 1.00(s, 3H), 1.10(s,   
                                 3H), 1.16(t, 3H), 1.50(q, 2H),           
       1.70(q, 2H), 2.2(s, 6H), 2.45˜                               
       2.9(m, 11H), 3.1(q, 2H),                                           
       4.5(s, 2H), 5.5(s, 2H), 10.5(br,                                   
       1H).                                                               
__________________________________________________________________________

                                  TABLE 3                                 
__________________________________________________________________________
                                        (1-c)                             
                                          #STR12##                        
   -                                                                      
Compound                                                                  
  No. R.sup.1 R.sup.2 R.sup.3 mp (° C.) .sup.1 H NMR (ppm)         
__________________________________________________________________________
38    CH.sub.3                                                            
         C.sub.2 H.sub.5                                                  
             CH.sub.3 Oil  1.15(s, 6H), 1.16(t, 3H), 2.17(s,              
       3H), 2.31(s, 3H), 2.45˜2.9(m,                                
       9H), 3.1(q, 2H), 3.92(s, 3H),                                      
       10.5(br, 1H).                                                      
  39 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Oil 1.15(s, 6H), 1.16(t,    
                           3H), 1.65(q,                                   
       2H), 2.17(s, 3H), 2.31(s, 3H),                                     
       2.45˜2.9(m, 9H), 3.1(q, 2H),                                 
       4.12(s, 3H), 10.5(br, 1H).                                         
  40 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 ═CHCH.sub.2 Oil 1.15(s, 6H),   
                           1.16(t, 3H), 2.17(s,                           
       3H), 2.31(s, 3H), 2.45˜2.9(m,                                
       9H), 4.60(dd, 2H), 5.1˜5.6(m,                                
       3H), 10.5(br, 1H).                                                 
  41 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 ═C(CH.sub.3)CH.sub.2 Oil       
                           1.15(s, 6H), 1.16(t, 3H), 1.56(d,              
       3H), 2.17(s, 3H), 2.31(s, 3H),                                     
       2.45˜2.9(m, 9H), 4.60(dd, 2H),                               
       5.1˜5.6(m, 2H), 10.5(br, 1H).                                
  42 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.3 Oil 0.97(t, 3H), 1.15(s, 6H),    
                           1.65(q,                                        
       2H), 2.17(s, 3H), 2.31(s, 3H),                                     
       2.45˜2.9(m, 9H), 3.1(q, 2H),                                 
       3.92(s, 3H), 10.5(br, 1H).                                         
  43 CH.sub.3 n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 Oil 1.0(t, 3H), 1.15(s,   
                           6H), 1.32(t, 3H),                              
       1.68(q, 2H), 2.12(s, 3H), 2.21(s,                                  
       3H), 2.50˜3.45(m, 10H), 3.80(s,                              
       1H), 4.0(q, 2H), 10.8(br, 1H).                                     
  44 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.2 ═CHCH.sub.2 Oil 0.97(t, 3H), 
                           1.15(s, 6H), 1.65(q,                           
       2H), 2.17(s, 3H), 2.31(s, 3H),                                     
       2.45˜2.9(m, 9H), 4.60(dd, 2H),                               
       5.1˜5.6(m, 3H), 10.5(br, 1H).                                
  45 CH.sub.3 n-C.sub.3 H.sub.7 CH.sub.2 ═C(CH.sub.3)CH.sub.2 Oil     
                           0.97(t, 3H), 1.15(s, 6H), 1.65(q,              
       2H), 2.17(s, 3H), 2.31(s, 3H),                                     
       2.45˜2.9(m, 9H), 4.60(dd, 2H),                               
       5.1˜5.6(m, 2H), 10.5(br, 1H).                                
  46 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 Oil 0.9(t, 3H), 1.07(s,     
                           3H), 1.16(t,                                   
       3H), 1.50(q, 2H), 2.12(s, 3H),                                     
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 3.92(s, 3H), 10.5(br,                                  
       1H).                                                               
  47 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 93˜94 0.9(t,   
                           3H), 1.07(s, 3H), 1.16˜                  
       1.21(m, 6H), 1.50(q, 2H),                                          
       2.12(s, 3H), 2.22(s, 3H), 2.45˜                              
       2.9(m, 11H), 3.1(q, 2H), 4.12(s,                                   
       3H), 10.5(br, 1H).                                                 
  48 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 ═CHCH.sub.2  0.9(t,     
                           3H), 1.07(s, 3H), 1.16(t,                      
       3H), 1.50(q, 2H), 2.12(s, 3H),                                     
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 4.55(dd, 2H), 5.1˜                               
       5.25(m, 2H), 10.5(br, 1H).                                         
  49 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ClCH═CHCH.sub.2  0.9(t, 3H),     
                           1.07(s, 3H), 1.16(t,                           
       3H), 1.50(q, 2H), 2.12(s, 3H),                                     
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 4.55(m, 2H), 5.1˜                                
       5.25(m, 2H), 10.5(br, 1H).                                         
  50 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 ═C(Cl)CH.sub.2 94˜
                           96 0.9(t, 3H), 1.07(s, 3H), 1.16(t,            
       3H), 1.50(q, 2H), 2.12(s, 3H),                                     
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 4.5(s, 2H), 5.5                                        
       (s, 2H), 10.5(br, 1H).                                             
  51 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.3 Oil 0.9(t, 3H), 1.00(s,   
                           3H), 1.10(s,                                   
       3H), 1.16(t, 3H), 1.50(q, 2H),                                     
       1.70(q, 2H), 2.12(s, 3H),                                          
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 3.92(s, 3H), 10.5(br,                                  
       1H).                                                               
  52 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 80˜82 1.0(t, 
                           3H), 1.15(s, 6H), 1.32(t,                      
       3H), 1.68(q, 2H), 2.12(s, 3H),                                     
       2.21(s, 3H), 2.50˜3.45(m, 10H),                              
       3.80(s, 1H), 4.0(q, 2H), 10.8(br,                                  
       1H).                                                               
  53 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.2 ═CHCH.sub.2 67˜6
                           9 0.9(t, 3H), 1.00(s, 3H), 1.10(s,             
       3H), 1.16(t, 3H), 1.50(q, 2H),                                     
       1.70(q, 2H), 2.12(s, 6H),                                          
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 4.55(dd, 2H), 5.1˜                               
       5.25(m, 3H), 10.5(br, 1H).                                         
  54 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 ClCH═CHCH.sub.2  0.9(t, 3H),   
                           1.00(s, 3H), 1.10(s,                           
       3H), 1.16(t, 3H), 1.50(q, 2H),                                     
       1.70(q, 2H), 2.12(s, 6H),                                          
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 4.55(dd, 2H), 5.1˜                               
       5.25(m, 2H), 10.5(br, 1H).                                         
  55 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 CH.sub.2 ═C(Cl)CH.sub.2        
                           0.9(t, 3H), 1.00(s, 3H), 1.10(s,               
       3H), 1.16(t, 3H), 1.50(q, 2H),                                     
       1.70(q, 2H), 2.12(s, 6H),                                          
       2.22(s, 3H), 2.45˜2.9(m, 11H),                               
       3.1(q, 2H), 4.5(s, 2H), 5.5(s,                                     
       2H), 10.5(br, 1H).                                                 
__________________________________________________________________________
Processes for preparing the present compounds of the formula (1) and the intermediates are illustrated further in the following examples.
EXAMPLE 1 5-(2,2,4,6,7-Pentamethylindan-5-yl)-2-[1-(allyloxyimino)propyl]-3-hydroxycyclohex-2-en-1-one.
i) 2,2,4,6,7-Pentamethylindan-1,3-dione.
To a mixture of 21.5 ml of 1,2,4-trimethylbenzene and 24.1 g of dimethylmalonyl chloride in 150 ml of dry dichloromethane was added slowly 38 mg of AlCl3 under the current of nitrogen gas at -10° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 g of ice, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 28.9 g of the title compound as a yellow solid.
Yield: 75%
mp: 58˜60° C.
1 H NMR(CDCl3): δ 1.15(s, 6H), 2.40(s, 3H), 2.6(s, 6H), 7.02(s, 1H)
ii) 2,2,4,6,7-Pentamethylindane
To a mixture of 100 g of 7% Zn/Hg in 200 ml of 20% hydrochloric acid and 70 ml of ethanol was added 22.32 g of the 2,2,4,6,7-pentamethylindan-1,3-dione with stirring. After refluxing for 6 hours, the reaction mixture was added 100 ml of benzene and refluxed for 1 hour. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 15.67 g of the title compound as yellow oil.
Yield: 81%
1 H NMR(CDCl3): δ 1.10(s, 6H), 2.05(s, 3H), 2.10(s, 3H), 2.55(s, 4H), 7.02(s, 1H)
iii) 2,2,4,6,7-Pentamethylindan-5-carboxaldehyde
To a solution of 24.5 g of the 2,2,4,6,7-pentamethylindane in 100 ml of dry dichloromethane was continuously added 18.5 ml of α,α-dichloromethyl methyl ether and 17.6 ml of TiCl4 at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 ml of water, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 26.8 g of the title compound as yellow solid.
yield: 95%
mp: 61˜62° C.
1 H NMR(CDCl3): δ 115(s, 6H), 2.10(s, 3H), 2.30(s, 3H), 2.35(s, 3H), 2.70(s, 4H), 10.5(s, 1H)
iv) 4-(2,2,4,6,7-Pentamethylindan-5yl)-3-buten-2-one
To a solution of 26.8 g of the 2,2,4,6,7-pentamethylindan-5-carboxaldehyde in 93 ml of absolute acetone was added 46 ml of water and 50 g of 2% NaOH. After refluxing for 20 hours, the solution was acidified with 2N HCl and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 25.36 g of the title compound as yellow solid.
yield: 79%
1 H NMR(CDCl3): δ 1.20(s, 6H), 2.20(s, 3H), 2.25(s, 6H), 2.35(s, 3H), 2.70(s, 4H), 5.9˜6.2(dd, 1H), 7.5˜7.7(dd, 1H)
v) 5-(2,2,4,6,7-Pentamethylindan-5-yl)-cyclohexane-1,3-dione.
To a solution of 3.25 g of sodium in 100 ml of absolute methanol was added 23 ml of diethyl malonate, and then the reaction mixture was added 25.3 g of 4-(2,2,4,6,7-pentamethylindan-5-yl)-3-buten-2-one in 50 ml of absolute methanol. After refluxing for 4 hours, the reaction mixture was evaporated under reduced pressure and then added 100 g of 10% aqueous solution of NaOH. After refluxing for 4 hours, the reaction mixture was cooled to room temperature and washed twice with diethyl ether. Concentrated hydrochloric acid was added dropwise into the boiling aqueous layers until the bubble of gas ceased and then the reaction mixture was cooled to room temperature. Solid product was collected and dried to afford 23.8 g of the title compound as white solid. mp: 63˜65° C.
1 H NMR(CDCl3): δ 1.17(s, 6H), 2.21(s, 3H), 2.25(s, 3H), 2.28(s, 3H), 2.40˜3.56(m, 7H), 5.30(s, 1H), 7.0(br, 1H)
vi) 5-(2,2,4,6,7-Pentamethylindan-5-yl)-2-propionyl-cyclohex-2-en-1-one.
To a solution of 14.7 g of the 5-(2,2,4,6,7-pentamethylindan-5-yl)-cyclohexane-1,3-dione in 100 ml of absolute toluene was added 25.6 ml of propionic anhydride. After refluxing for 4 hours, toluene and excess propionic anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 1.22 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 10.1 g of the title compound as yellow solid.
mp: 108˜109° C.
1 H NMR(CDCl3): δ 1.20(t, 3H), 1.20(s, 6H), 2.17(s, 3H), 2.25(s, 3H), 2.75(s, 3H), 2.50˜3.40(m, 9H), 3.80˜4.0(m, 1H), 10.8(br, 1H)
vii) 5-(2,2,4,6,7-Pentamethylindan-5-yl)-2-butyryl-cyclohex-2-en-1-one.
To a solution 14.7 g of the 5-(2,2,4,6,7-pentamethylindan-5-yl)-cyclohexane-1,3-dione in 100 ml of absolute toluene was added 32.7 ml of butyric anhydride. After refluxing for 4 hours, toluene and excess butyric anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 1.22 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 10.84 g of the title compound as yellow solid.
mp: 85˜86° C.
1 H NMR(CDCl3): δ 1.0(t, 3H), 1.15(s, 6H), 1.70(q, 2H), 2.10(s, 3H), 2.25(s, 3H), 2.30(s, 3H), 2.50˜3.45(m, 10H), 3.80˜4.0(s, 1H), 10.8(br, 1H)
viii) 5-(2,2,4,6,7-pentamethylindan-5-yl)-2-[1-(allyloxyimino)pyropyl]-3-hydroxycyclohex-2-en-1-one
To a solution 0.35 g of the 5-(2,2,4,6,7-pentamethylindan-5-yl)-2-propionyl-cyclohex-2-en-1-one in 10 ml of ethanol was added 0.16 g of sodium acetate (NaOAc.3H2 O) and 0.13 g of allyloxylamine. After stirring at room temperature for 10 hours, the reaction mixture extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 0.43 g of the title compound as yellow foam.
1 H NMR(CDCl3): δ 1.20(t, 3H), 1.20(s, 6H), 2.17(s, 3H), 2.25(s, 3H), 2.75(s, 3H), 2.50˜3.40(m, 10H), 3.80˜4.0(m, 1H), 4.6(d, 2H), 5.5(dd, 2H), 5.8˜6.2(m, 1H), 10.8(br, 1H)
EXAMPLE 2
5-(2-Ethyl-2,4,5,7-tetramethylindan-6-yl)-2-[1-(allyloxyimino)propyl]-3-hydroxycyclohex-2-en-1-one.
i) 2-Ethyl-2,4,5,7-tetramethylindan-1,3-dione.
To a mixture of 18.0 ml of 1,2,4-trimethylbenzene and 22.8 g of ethylmethylmalonyl chloride in 200 ml of dry dichloromethane was added slowly 32 g of AlCl3 under the current of nitrogen gas at -10° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 g of ice, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 26 g of the title compound as a yellow solid.
Yield: 93%
bp: 94˜95° C./0.01 torr
1 H NMR(CDCl3): δ 0.7(t, 3H), 1.20(s, 3H), 1.71(q, 2H), 2.44(s, 3H), 2.68(s, 6H), 7.3(s, 1H)
ii) 2-Ethyl-2,4,5,7-tetramethylindane
To a mixture of 60 g of 7% Zn/Hg in 200 ml of 20% hydrochloric acid and 70 ml of ethanol was added 27.92 g of the 2-ethyl-2,4,5,7-tetramethylindan-1,3-dione with stirring. After refluxing for 6 hours, the reaction mixture was added 100 ml of benzene and refluxed for 3 hour. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 17.77 g of the title compound as yellow oil.
Yield: 72.4%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.52(q, 2H), 2.11(s, 3H), 2.21(s, 6H), 2.92(s, 4H), 6.61(s, 1H)
iii) 2-Ethyl-2,4,5,7-tetramethylindan-6-carboxaldehyde
To a solution of 17.7 g of the 2-ethyl-2,4,5,7-tetramethylindane in 100 ml of dry dichloromethane was continuously added 9.5 ml of α,α-dichloromethyl methyl ether and 11.6 ml of TiCl4 at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 ml of water, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 18.26 g of the title compound as brown solid.
yield: 90%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.52(q, 2H), 2.11(s, 3H), 2.20(s, 3H), 2.22(s, 3H), 2.85(s, 4H), 10.5(s, 1H)
iv) 4-(2-Ethyl-2,4,5,7-tetramethylindan-6-yl)-3-butene-2-one
To a solution of 18.26 g of the 2-ethyl-2,4,5,7-tetramethylindan-6-carboxaldehyde in 58 ml of absolute acetone was added 28 ml of water and 32 g of 2% NaOH. After refluxing for 20 hours, the solution was acidified was 2N HCl and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 19.38 g of the title compound as yellow oil.
yield: 79%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.52(q, 2H), 2.10(s, 3H), 2.11(s, 3H), 2.20(s, 3H), 2.22(s, 3H), 2.85(s, 4H), 6.2(dd, 1H), 7.5˜7.7(dd, 1H)
v) 5-(2-Ethyl-2,4,5,7-tetramethylindan-6-yl)-cyclohexane-1,3-dione.
To a solution of 2.47 g of sodium in 100 ml of absolute methanol was added 16.3 ml of diethyl malonate, and then the reaction mixture was added 19.38 g of 4-(2-ethyl-2,4,5,7-tetramethylindan-6-yl)-3-buten-2-one in 50 ml of absolute methanol. After refluxing for 4 hours, the reaction mixture was evaporated under reduced pressure and then added 115 g of 10% aqueous solution of NaOH. After refluxing for 4 hours, the reaction mixture was cooled to room temperature and washed twice with diethyl ether. Concentrated hydrochloric acid was added dropwise into the boiling aqueous layers until the bubble of gas ceased and then the reaction mixture was cooled with room temperature. Solid product was collected and dried to afford 22.0 g of the title compound.
Yield: 98.6%
1 H NMR(CDCl3): δ 0.95(t, 3H), 1.05(s, 3H), 1.52(q, 2H), 2.20(s, 3H), 2.30(s, 3H), 2.32(s, 3H), 2.40˜3.36(m, 7H), 5.30(s, 1H), 9.5(br, 1H)
vi) 5-(2-Ethyl-2,4,5,7-tetramethylindan-6-yl)-2-propionyl-cyclohex-2-en-1-one.
To a solution of 7.8 g of the 5(2-ethyl-2,4,5,7-pentamethylindan-6-yl)-cyclohexane-1,3-dione in 70 ml of absolute toluene was added 12.8 ml of propionic anhydride. After refluxing for 4 hours, toluene and excess propionic anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.61 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 4.19 g of the title compound as yellow solid
Yield: 45.5%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.10(s, 3H), 1.18(t, 3H), 1.52(q, 2H), 2.17(s, 3H), 2.25(s, 3H), 2.30(s, 3H), 2.52˜2.50(m, 6H), 3.05˜3.47(m, 4H), 3.80˜4.05(m, 1H), 11.2(br, 1H)
vii) 5-(2-Ethyl-2,4,5,7-tetramethylindan-6-yl)-2-butyryl-cyclohex-2-en-1-one.
To a solution 7.8 g of the 5-(2-ethyl-2,4,5,7-tetramethylindan-6-yl)-cyclohexane-1,3-dione in 100 ml of absolute toluene was added 16.4 ml of butyric anhydride. After refluxing for 4 hours, toluene and excess butyric anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.61 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 44.43 g of the title compound as yellow solid.
Yield: 46.3%
mp: 69˜71° C.
1 H NMR(CDCl3): δ 0.90(t, 3H), 1.10(s, 3H), 1.18(t, 3H), 1.52(q, 2H), 1.67(m, 2H), 2.17(s, 3H), 2.25(s, 3H), 2.30(s, 3H), 2.52˜2.50(m, 6H), 3.05˜3.47(m, 4H), 3.80˜4.05(m, 1H), 11.2(br, 1H)
viii) 5-(2-Ethyl-2,4,5,7-tetramethylindan-6-yl)-2-[1-(allyloxyimino)propyl]-3-hydroxycyclohex-2-en-1-one
To a solution 0.37 g of the 5-(2-ethyl-2,4,5,7-tetramethylindan-6-yl)-2-propionyl-cyclohex-2-end-1-one in 10 ml of ethanol was added 0.16 g of sodium acetate (NaOAc.3H2 O) and 0.13 g of allyloxylamine hydrochloride. After stirring at room temperature for 10 hours, the reaction mixture extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 0.35 g of the title compound as yellow solid.
mp: 64˜65° C.
1 H NMR(CDCl3): δ 0.90(t, 3H), 1.10(s, 3H), 1.18(t, 3H), 1.52(q, 2H), 2.17 (s, 3H), 2.25(s, 3H), 2.30(s, 3H), 2.52˜2.50(m, 6H), 3.05˜3.47(m, 4H), 3.80˜4.05(m, 1H), 4.5(d, 2H), 5.15˜5.50(m, 2H), 5.6˜6.2(m, 1H), 11.2(br, 1H)
EXAMPLE 3
5-(6-Chloro-2,2,4,7-tetramethylindan-5-yl)-2-[1-(ethoxyimino)butyl]-3-hydroxycyclohex-2-en-1-one.
i) 6-Chloro-2,2,4,7-tetramethylindan-1,3-dione.
To a mixture of 30 ml of 2-chloro-p-xylene and 24.38 g of dimethylmalonyl chloride in 150 ml of dry dichloromethane was added slowly 38 g of AlCl3 under the current of nitrogen gas at -10° C. The reaction mixture was stirred at room temperature of 2 hours, quenched with 200 g of ice, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 27.4 g of the title compound as a yellow solid.
Yield: 79.6%
1 H NMR(CDCl3): δ 1.3(s, 6H), 2.40(s, 3H), 2.7(s, 3H), 7.62(s, 1H)
ii) 6-Chloro-2,2,4,7-tetramethylindane
To a mixture of 100 g of 7% Zn/Hg in 200 ml of 20% hydrochloric acid and 70ml of ethanol was added 27.32 g of the 6-chloro-2,2,4,7-tetramethylindan-1,3-dione with stirring. After refluxing for 6 hours, the reaction mixture was added 100 ml of benzene and refluxed for 1 hour. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 15.67 g of the title compound as yellow oil.
Yield: 81%
1 H NMR(CDCl3): δ 1.20(s,6H), 2.10(s, 3H), 2.25(s, 3H), 2.65(s, 4H), 6.90(s, 1H)
iii) 6-Chloro-2,2,4,7-tetramethylindan-5-carboxaldehyde
To a solution of 19.8 g of the 6-chloro-2,2,4,7-tetramethylindane in 100 ml of dry dichloromethane was continuously added 13 ml of α,α-dichloromethyl methyl ether and 12.4 ml of TiCl4 at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 ml of water, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 21.8 g of the title compound as yellow solid.
yield: 83.3%
mp: 127° C.
1 H NMR(CDCl3): δ 1.20(s, 6H), 2.3(s, 3H), 2.35(s, 3H), 2.36(s, 3H), 2.75(s, 4H), 10.8(s, 1H)
iv) 4-(6-Chloro-2,2,4,7-tetramethylindan-5-yl)-3-buten-2-one
To a solution of 21.8 g of the 6-chloro-2,2,4,7-tetramethylindan-5-carboxaldehyde in 67 ml of absolute acetone was added 33 ml of water and 36.5 g of 2% NaOH. After refluxing for 20 hours, the solution was acidified with 2N HCl and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 16.6 g of the title compound as yellow solid.
yield: 65%
1 H NMR(CDCl3): δ 1.20(s, 6H), 2.20(s, 3H), 2.30(s, 6H), 2.35(s, 3H), 2.70(s, 4H). 6.1˜6.3(dd, 1H), 7.45˜7.60(dd, 1H)
v) 5-(6-Chloro-2,2,4,7-tetramethylindan-5-yl)-cyclohexane-1,3-dione.
To a solution of 1.9 g of sodium in 100 ml of absolute methanol was added 14 ml of diethyl malonate, and then the reaction mixture was added 16.6 g of 4-(6-chloro-2,2,4,7-tetramethylindan-5-yl)-3-buten-2-one in 50 ml of absolute methanol. After refluxing for 4 hours, the reaction mixture was evaporated under reduced pressure and then added 100 g of 10% aqueous solution of NaOH. After refluxing for 4 hours, the reaction mixture was cooled to room temperature and washed twice with diethyl ether. Concentrated hydrochloric acid was added dropwise into the boiling aqueous layers until the bubble of gas ceased and then the reaction mixture was cooled to room temperature. Solid product was collected and dried to afford 19 g of the titile compound as yellow solid.
mp: 129˜139° C.
1 H NMR(CDCl3): δ 1.15(s, 6H), 2.21(s, 3H), 2.23(s, 3H), 2.7(s, 4H), 240˜3.56(m, 9H, 5.30(s, 1H), 7.8(br, 1H)
vi) 5-(Chloro-2,2,4,7-tetramethylindan-5-yl)-2-propionyl-cyclohex-2-en-1-one.
To a solution of 8.02 g of the 5-(6-chloro-2,2,4,7-tetramethylindan-5-yl)-cyclohexane-1,3-dione in 100 ml of absolute toluene was added 12.8 ml of propionic anhydride. After refluxing for 4 hours, toluene and excess propionicanhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.61 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 10.1 g of the title compound as yellow solid.
mp: 125˜127° C.
1 H NMR(CDCl3): δ 1.15(t, 3H), 1.15(s, 6H), 2.10(s, 3H), 2.12(s, 3H), 2.50˜3.40(m, 10H), 3.80˜4.0(m, 1H), 10.8(br, 1H)
vii) 5-(6-Chloro-2,2,4,7-tetramethylindan-5-yl)-2-butyryl-cyclohex-2-en-1-one.
To a solution 8.02 g of the 5-(6-chloro-2,2,4,7-tetramethylindan-5-yl)-cyclohexane-1,3-dione in 100 ml of absolute toluene was added 13.4 ml of butyric anhydride. After refluxing for 4 hours, toluene and excess butyric anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.61 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 3.51 g of the title compound as yellow solid.
Yield: 36%
mp: 93˜94° C.
1 H NMR(CDCl3): δ 1.0(t, 3H), 1.15(s, 6H), 1.68(q, 2H), 2.12(s, 3H), 2.21(s, 3H), 2.50˜3.45(m, 10H), 3.80˜4.0(s, 1H), 10.8(br, 1H)
vii) 5-(6-Chloro-2,2,4,7-tetramethylindan-5-yl)-2-[1-(ethoxyimino)butyl]-3-hydroxycyclohex-2-en-1-one
To a solution 0.39 g of the 5-(6-chloro-2,2,4,7-tetramethylindan-5-yl)-2-propionyl-cyclohex-2-en-1-one in 10 ml of ethanol was added 0.16 g of sodium acetate (NaOAc.3H2 O) and 0.13 g of ethoxylamine. After stirring at room temperature for 10 hours, the reaction mixture extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 0.553 g of the title compound as yellow foam.
1 H NMR(CDCl3): δ 1.0(t, 3H), 1.15(s, 6H), 1.32(t, 3H), 1.68(q, 2H), 2.12(s, 3H), 2.21(s, 3H), 2.50˜3.45(m, 10H), 3.80(s, 3H), 4.0(q, 2H), 10.8(br, 1H)
EXAMPLE 4
5-(6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-2-[1-(ethoxyimino)propyl]-3-hydroxycyclohex-2-en-1-one.
i) 6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl-1,3-dione.
To a mixture of 24 ml of 4-chloro-p-xylene and 31.3 g of ethylmethylmalonyl chloride in 250 ml of dry dichloromethane was added slowly 34.4 g of AlCl3 under the current of nitrogen gas at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 g of ice, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 33.1 g of the title compound as a yellow solid.
Yield: 81.6%
mp: 95˜96° C.
1 H NMR(CDCl3): δ 0.8(t, 3H), 1.2(s, 3H), 1.8(q, 2H), 2.75(s, 3H), 2.83(s, 3H), 7.62(s, 1H)
ii) 6-Chloro-2-ethyl-2,4,7-trimethylindane
To a mixture of 83 g of 7% Zn/Hg in 70 ml of 20% hydrochloric acid and 70 ml of ethanol was added 40.0 g of the 6-chloro-2-ethyl-2,4,7-trimethylindan-5-yl-1,3-dione with stirring. After refluxing for 6 hours, the reaction mixture was added 100 ml of benzene and refluxed for 1 hour. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 19.4 g of the title compound as yellow oil.
Yield: 52.5%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.5(t, 2H), 2.21(s, 3H), 2.27(s, 3H), 2.6(s, 4H), 7.62(s, 1H)
iii) 6-Chloro-2-ethyl-2,4,7-trimethylindan-5-carboxaldehyde
To a solution of 19 g of the 6-chloro-2-ethyl-2,4,7-trimethylindane in 100 ml of dry dichloromethane was continuously added 9.5 ml of α,α-dichloromethyl methyl ether and 11.5 ml of TiCl4 at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 100 ml of water, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 20.85 g of the title compound as yellow solid.
yield: 97%
mp: 89˜90° C.
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.5(q, 2H), 2.21(s, 3H), 2.45(s, 3H), 2.8(s, 4H), 10.65(s, 1H).
iv) 4-(6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-3-buten-2-one
To a solution of 24.35 g of the 6-chloro-2-ethyl-2,4,7-trimethylindan-5-carboxaldehyde in 73 ml of absolute acetone was added 36 ml of water and 40 g of 2% NaOH. After refluxing for 20 hours, the solution was acidified with 2N HCl and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 22.08 g of the title compound as brown oil.
yield: 78%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.5(q, 2H), 2.10(s, 3H), 2.21(s, 3H), 2.35(s, 3H), 2.8(s, 4H), 6.1˜6.3(dd, 1H), 7.45˜7.60(dd, 1H)
v) 5-(6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-cyclohexane-1,3-dione.
To a solution of 2.7 g of sodium in 100 ml of absolute methanol was added 100 ml of diethyl malonate, and then the reaction mixture was added 22.08 g of 4-(6-chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-3-buten-2-one in 50 ml of absolute methanol. After refluxing for 4 hours, the reaction mixture was evaporated under reduced pressure and then added 12.3 g of 10% aqueous solution of NaOH. After refluxing for 4 hours, the reaction mixture was cooled to room temperature and washed twice with diethyl ether. Concentrated hydrochloric acid was added dropwise into the boiling aqueous layers until the bubble of gas ceased and then the reaction mixture was cooled to room temperature. Solid product was collected and dried to afford 23 g of the titile compound as yellow solid.
mp: 79˜80° C.
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.5(q, 2H), 2.20(s, 3H), 2.21(s, 3H), 2.40˜2.85(m, 9H), 3.5˜4.1(m, 1H), 5.30(s, 1H), 9.5(br, 1H).
vi) 5-(6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-2-propionyl-cyclohex-2-en-1-one.
To a solution of 9.3 g of the 5-(6-chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-cyclohexane-1,3-dione in 50 ml of absolute toluene was added 15 ml of propionic anhydride. After refluxing for 4 hours, toluene and excess propionic anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 50 ml of toluene was added 0.6 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 4.96 g of the title compound as yellow solid.
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.15(t, 3H), 1.5(q, 2H), 2.20(s, 3H), 2.21(s, 3H), 2.40˜2.85(m, 11H), 3.5˜4.1(m, 1H), 5.30(s, 1H), 9.5(br, 1H).
vii) 5-(6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-2-buryryl-cyclohex-2-en-1-one.
To a solution 9.3 g of the 5-(6-chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-cyclohexane-1,3-dione in 50 ml of absolute toluene was added 19 ml of buryric anhydride. After refluxing for 4 hours, toluene and excess butyric anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.6 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 4.10 g of the title compound as yellow solid.
Yield: 36%
mp: 56˜58° C.
1 H NMR(CDCl3): δ 1.0(t, 3H), 1.15(s, 6H), 1.52(t, 3H), 1.68(m, 2H), 2.120(s, 3H), 2.21(s, 3H), 2.50˜3.45(m, 10H), 3.80˜4.0(s, 1H), 10.8(br, 1H)
viii) 5-(6-Chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-2-[1-(ethoxyimino)propyl]-3-hydroxycyclohex-2-en-1-one
To a solution 0.15 g of the 5-(6-chloro-2-ethyl-2,4,7-trimethylindan-5-yl)-2-propionyl-cyclohex-2-en-1-one in 10 ml of ethanol was added 0.9 g of sodium acetate (NaOAc.3H2 O) and 0.64 g of ethoxylamine hydrochloride. After stirring at room temperature for 10 hours, the reaction mixture extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 0.1153 g of the title compound as yellow oil.
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.05(s, 3H), 1.12(t, 3H), 1.15(t, 3H), 1.5(q, 2H), 2.20(s, 3H), 2.21(s, 3H), 2.40˜2.85(m, 11H), 3.5˜4.0(m, 1H), 4.15(q, 2H), 5.30(s, 1H), 9.5(br, 1H).
EXAMPLE 5
5-(7-Chloro-2,2,4,5-tetramethylindan-6-yl)-2-[1-(ethoxyimino)butyl]-3-hydroxycyclohex-2-en-1-one.
i) 7-Chloro-2,2,4,5-tetramethylindan-1,3-dione
To a mixture of 35.5 ml of 4-chloro-o-xylene and 29.84 g of dimethylmalonyl chloride in 150 ml of dry dichloromethane was added slowly 34.7 g of AlCl3 under the current of nitrogen gas at -10° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 g of ice, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 34.99 g of the title compound as yellow solid.
Yield: 83%
1 H NMR(CDCl3): δ 1.26(s, 6H), 2.45(s, 3H), 2.65(s, 3H), 7.50(s, 1H)
ii) 7-Chloro-2,2,4,5-tetramethylindane
To a mixture of 100 g of 7% Zn/Hg in 200 ml of 20% hydrochloric acid and 70 ml of ethanol was added 38.42 g of the 7-chloro-2,2,4,5-tetramethylindan-1,3-dione with stirring. After refluxing for 6 hours, the reaction mixture was added 100 ml of benzene and refluxed for 1 hour. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 17.0 g of the title compound as yellow oil.
Yield: 50%
1 H NMR(CDCl3): δ 1.20(s, 6H), 2.10(s, 3H), 2.20(s, 3H), 2.70(dd, 4H), 6.90(s, 1H)
iii) 7-Chloro-2,2,4,5-tetramethylindan-6-carboxaldehyde
To a solution of 17.0 g of the 7-chloro-2,2,4,5-tetramethylindane in 100 ml of dry dichloromethane was continuously added 18.5 ml of α,α-dichloromethyl methyl ether and 11 ml of TiCl2 at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 ml of water, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 14.7 g of the title compound as yellow solid.
yield: 76.6%
mp: 108° C.
1 H NMR(CDCl3): δ 1.30(s, 6H), 2.20(s, 3H), 2.45(s, 3H), 2.35(s, 3H), 2.85(s, 4H), 10.8(s, 1H)
iv) 4-(7-Chloro-2,2,4,5-tetramethylindan-6-yl)-3-buten-2-one
To a solution of 14.7 g of the 7-chloro-2,2,4,5-tetramethylindan-6-carboxaldehyde in 48 ml of absolute acetone was added 23 ml of water and 25 g of 2% NaOH. After refluxing for 20 hours the solution was acidified with 2N HCl extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 5.35 g of the title compound as yellow solid.
yield: 35%
1 H NMR(CDCl3): δ 1.20(s, 6H), 2.15(s, 3H), 2.26(s, 6H), 2.30(s, 3H), 2.80(s, 4H), 615˜6.4(dd, 1H), 7.45˜7.70(dd, 1H)
v) 5-(7-Chloro-2,2,4,5-tetramethylindan-6-yl)-cyclohexane-1,3-dione
To a solution of 1.3 g of sodium in 50 ml of absolute methanol was added 8 ml of diethyl malonate, and then the reaction mixture was added 9.41 g of 5-(5-chloro-2,2,4,7-tetramethylindan-6-yl)-3-buten-2-one in 50 ml of absolute methanol. After refluxing for 4 hours, the reaction mixture was evaporated under reduced pressure and then added 100 g of 10% aqueous solution of NaOH. After refluxing for 4 hours, the reaction mixture was cooled to room temperature and washed twice with diethyl ether. Concentrated hydrochloric acid was added dropwise into the boiling aqueous layers until the bubble of gas ceased and then the reaction mixture was cooled to room temperature. Solid product was collected and dried to afford 9.24 g of the titile compound as white solid.
Yield: 77%
1 H NMR(CDCl3): δ 1.15(s, 6H), 2.21(s, 3H), 2.23(s, 3H), 2.7(s, 4H), 240˜356(m, 9H), 5.30(s, 1H), 7.8(br, 1H)
vi) 5-(7-Chloro-2,2,4,5-tetramethylindan-6-yl)-2-propionyl-cyclohex-2-en-1-one
To a solution of 4.52 g of the 5-(7-chloro-2,2,45-tetramethylindan-6-yl)-cyclohexane-1,3-dione in 70 ml of absolute toluene was added 7.2 ml of propionic anhydride. After refluxing for 4 hours, toluene and excess propionic anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.35 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 2.13 g of the title compound as yellow solid.
mp: 74˜75° C.
1 H NMR(CDCl3): δ 1.15(t, 3H), 1.15(s, 6H), 2.10(s, 3H), 2.12(s, 3H), 250˜3.40(m, 10H), 3.80˜4.0(m, 1H), 10.8(br, 1H)
vii) 5-(7-Chloro-2,2,4,5-tetramethylindan-6-yl)-2-butyryl-cyclohex-2-en-1-one
To a solution 4.62 g of the 5-(7-chloro-2,2,4,5-tetramethylindan-6-yl)-cyclohexane-1,3-dione in 100 ml of absolute toluene was added 9.4 ml of butyric anhydride. After refluxing for 4 hours, toluene and excess butyric anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.35 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 2.15 g of the title compound as yellow solid.
Yield: 38%
1 H NMR(CDCl3): δ 1.0(t, 3H), 1.15(s, 6H), 1.68(q, 2H), 2.120(s, 3H), 2.21(s, 3H), 2.50˜3.45(m, 10H), 3.80˜4.0(s, 1H), 10.8(br, 1H)
viii) 5-(7-Chloro-2,2,4,5-tetramethylindan-6-yl)-2-[1-(ethoxyimino)butyl]-3-hydroxycyclohex-2-en-1-one
To a solution 0.39 g of the 5-(7-chloro-2,2,4,5-tetramethylindan-6-yl)-2-propionyl-cyclohex-2-en-1-one in 10 ml of ethanol was added 0.16 g of sodium acetate (NaOAc.3H2 O) and 0.13 g of ethoxylamine hydrochloride. After stirring at room temperature for 10 hours, the reaction mixture extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered ande vaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 0.29 g of the title compound as yellow foam.
1 H NMR(CDCl3): δ 1.0(t, 3H), 1.15(s, 6H), 1.32(t, 3H), 1.68(q, 2H), 2.120(s, 3H), 2.21(s, 3H), 2.50˜3.45(m, 10H), 3.80(s, 1H), 4.0(q, 2H), 10.8(br, 1H)
EXAMPLE 6
5-(7-Chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-2-[1-(ethoxyimino)propyl]-3 hydroxycyclohex-2-en-1-one.
i) 7-Chloro-2-ethyl-2,4,5-trimethylindan-1,3-dione
To a mixture of 28 ml of 4-chloro-o-xylene and 37.6 g of ethylmethylmalonyl chloride in 300 ml of dry dichloromethane was added slowly 26.7 g of AlCl3 under the current of nitrogen gas at -10° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 200 g of ice, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 24.67 g of the title compound as a yellow solid.
Yield: 50%
mp: 97° C.
1 H NMR(CDCl3): δ 0.7(t, 3H), 1.27(s, 3H), 1.80(t, 2H), 2.46(s, 3H), 2.70(s, 3H), 7.80(s, 1H)
ii) 7-Chloro-2-ethyl-2,4,5-trimethylindane
To a mixture of 66 g of 7% Zn/Hg in 70 ml of concentrated hydrochloric acid and 70 ml of ethanol was added 24.67 g of the 7-chloro-2-ethyl-2,4,5-trimethylindan-13-dione with stirring. After refluxing for 6 hours, the reaction mixture was added 100 ml of benzene and refluxed for 1 hour. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 9.23 g of the title compound as yellow oil.
Yield: 42%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.12(s, 3H), 1.45(t, 2H), 2.05(s, 3H), 2.26(s, 3H), 2.7(s, 4H), 6.80(s, 1H)
iii) 7-Chloro-2-ethyl-2,4,5,-trimethylindan-6-carboxaldehyde
To a solution of 9.98 g of the 7-chloro-2-ethyl-2,4,5-trimethylindane in 100 ml of dry dichloromethane was continuously added 6.2 ml of α,α-dichloromethyl methyl ether and 7.5 ml of TiCl4 at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 100 ml of water, and separated the organic layer. The aqueous layer was extracted with dichloromethane. The combined organic layer was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 9.23 g of the title compound as yellow solid.
yield: 82%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.12(s, 3H), 1.45(t, 2H), 2.05(s, 3H), 2.26(s, 3H), 2.7(s, 4H), 10.80(s, 1H)
iv) 4-(7-Chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-3-buten-2-one
To a solution of 14.7 g of the 7-chloro-2-ethyl-2,4,5-trimethylindan-6-carboxaldehyde in 45 ml of absolute acetone was added 22 ml of water and 24 g of 2% NaOH. After refluxing for 20 hours, the solution was acidified with 2N HCl and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 12.65 g of the title compound as brown oil.
yield: 73.7%
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.12(s, 3H), 1.45(t, 2H), 2.05(s, 3H), 2.10(s, 3H), 2.26(s, 3H), 2.7(s, 4H), 615˜6.4(dd, 1H), 7.45˜7.70(dd, 1H)
v) 5-(7-Chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-cyclohexane-1,3-dione
To a solution of 1.53 g of sodium in 100 ml of absolute methanol was added 10 ml of diethyl malonate, and then the reaction mixture was added 12.65 g of 4-(5-chloro-2,2,4,7-tetramethylindan-6-yl)-3-buten-2-one in 50 ml of absolute methanol. After refluxing for 4 hours, the reaction mixture was evaporated under reduced pressure and then added 70 g of 10% aqueous solution of NaOH. After refluxing for 4 hours, the reaction mixture was cooled to room temperature and washed twice with diethyl ether. Concentrated hydrochloric acid was added dropwise into the boiling aqueous layers until the bubble of gas ceased and then the reaction mixture was cooled to room temperature. Solid produce was collected and dried to afford 11.9 g of the titile compound as yellow solid.
Yield: 87%
1 H NMR(CDCl3): δ 0.95(t, 3H), 1.0(s, 3H), 1.5(t, 2H), 2.10(s, 3H), 2.26(s, 3H), 2.40˜3.56(m, 9H), 5.30(s, 1H), 10.5(br, 1H).
vi) 5-(7-Chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-2-propionyl-cyclohex-2-en-1-one
To a solution of 7.12 g of the 5-(7-chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-cyclohexane-1,3-dione in 70 ml of absolute toluene was added 11.8 ml of propionic anhydride. After refluxing for 4 hours, toluene and excess propionic anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.56 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 4.53 g of the title compound as yellow solid.
Yield: 54%
mp: 55˜57° C.
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.07(s, 3H), 1.15(t, 3H), 1.50(t, 2H), 2.15(s, 3H), 2.25(s, 3H), 2.40˜2.87(m, 9H), 3.08(q, 2H), 5.30(s, 1H), 10.5(br, 1H).
vii) 5-(7-Chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-2-butyryl-cyclohex-2-en-1-one
To a solution 7.12 g of the 5-(7-chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-cyclohexane-1,3-dione in 70 ml of absolute toluene was added 15 ml of buryric anhydride. After refluxing for 4 hours, toluene and excess butyric anhydride were evaporated under reduced pressure to afford a residue. To the solution of the residue in 100 ml of toluene was added 0.56 g of dimethylaminopyridine and refluxed for 20 hours. The reaction mixture was evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 4.64 g of the title compound as yellow solid.
Yield: 53%
mp: 45˜47
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.07(s, 3H), 1.15(t, 3H), 1.50(t, 2H), 1.68(m, 2H), 2.15(s, 3H), 2.25(s, 3H), 2.40˜2.87(m, 9H), 3.08(q, 2H), 5.30(s, 1H), 10.5(br, 1H).
viii) 5-(7-Chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-2-[1-(ethoxyimino)propyl]-3-hydroxycyclohex-2-en-1-one
To a solution 0.37 g of the 5-(7-chloro-2-ethyl-2,4,5-trimethylindan-6-yl)-2-propionyl-cyclohex-2-en-1-one in 10 ml of ethanol was added 0.16 g of sodium acetate (NaOAc.3H2 O) and 0.13 g of ethoxylamine hydrochloride. After stirring at room temperature for 10 hours, the reaction mixture extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography to afford 0.338 g of the title compound as yellow solid.
mp: 93˜94° C.
1 H NMR(CDCl3): δ 0.9(t, 3H), 1.07(s, 3H), 1.15(t, 3H), 1.22(t, 3H), 1.50(t, 2H), 2.15(s, 3H), 2.25(s, 3H), 2.40˜2.87(m, 9H), 3.08(q, 2H), 4.0(q, 2H), 10.5(br, 1H).
Novel cyclohexane-1,3-dione derivatives of the formula(1) according to the present invention are sufficiently tolerant on most broad leaved plant such as soybeans, cotton, sunflower, sugarbeet and various kings of vegetables and may be available for post-emergent control of grassy weeds in said crops.
The compounds of formula(1) according to the present invention may be applied for instance in form of wettable powders, dust, flowable concentrates, granules, solutions or emulsifiable concentrates.
The content of the compound of the formula(1) is usually from 0.1 to 95% by weight for these formulations in order to get sufficient effects as herbicides and plant-growth regulants.
To prepare the above formulations it can be used either solid carrier or liquid carrier. As solid carriers, inorganic powders such as kaolinite, bentonite, montmorillonite, talc diatomaceous earth, mica, gypsum, calcium carbonate, apatite, synthesized silicon hydroxide hydrate; plant powders such as soy powder, wheat powder, sawdust, tabacco powder, starch powder, crystallized cellulose; polymers such as petroleum resin, vinyl chloride resin, ketone resin; alumina or beeswax etc. can be used.
As liquid carriers, alcohols such as methanol, ethanol, ethylene glycol, benzyl alcohol; aromatic hydrocarbons such as toluene, benzene, xylene, methyl naphthalene, halohydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene; ethers such as dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyleneglycol acetate; amides such as dimethyl formamide; nitriles such as acetonitrile; ether alcohols such as ethylene glycol, diethyl ethers or water etc. can be used.
Surfactants can be advantageously employed herein such as various cationic, anionic and nonionic surfactants.
Cationic surfactants include long chain alkylammonium salts such as cetyltrimethylammonium bromide, etc.
Anionic surfactants include alkali metal, alkaline earth metal and ammonium salts of alkylarylsulfonic acids such as dodecylbenzenesulfonic acid; alkylsulfonic acids; alkylsulfuric acids such as laurylsulfuric acid; ligninsulfonic acid; arylsulfonic acids such as naphthalenesulfonic acid or dibutylnaphthalenesulfonic acid; lauryl ether sulfate; fatty alcohol sulfates; fatty acids; salts of sulfated hexadecanols, heptadecanols or octadecanois; salts of sulfated fatty alcohol glycol ethers, etc.
Examples of nonionic surfactants include condensation products of fatty alcohols such as oleyl alcohol or cetyl alcohol; phenols; alkylphenols or caster oil with ethylene oxide or propylene oxide; condensation products of naphthalene or naphthalene sulfonic acids with phenol or formaldehyde, etc.
The application amount of compound represented by the formula(1) is from 0.06 kg to 8 kg/ha, preferably from 0.25 kg to 1 kg/ha.
The active herbicidal compounds of this invention may be formulated with insecticides, fungicides, nematocides, plant growth regulators, fertilizers, other herbicides or other agricultural chemicals.
TEST: Herbicidal Activity Evaluation
The herbicidal activity test is proceeded according to the following methods.
The sterilized sandy loam soil is filled in test pot having a surface area of 348 cm2 for upland test conditions or 115 cm2 for paddy test species were planted in furrows.
For the pre-emergent tests, were sprayed on the soil one day after planting test compound in a mixture of acetone and 7 ml of the water containing up to 0.1% Tween 20.
The concentration of the test compound in solution was varied to give a range of application rates, generally 4.0 kg/ha and submultiples thereof. The pots were placed in a greenhouse and watered regularly at the soil surface for 21 days and herbicidal effects were visually rated by a percent control.
The pots for the post-emergent tests were placed in a greenhouse and watered for 9˜14 days, then the foliage of test plants was sprayed with a solution of the test compound in a mixture of acetone and water containing a small amount of Tween 20.
After spraying the plants were kept for one day, then watered regularly for 14 to 21 days, and herbicidal activity data were recorded.
The herbicidal activity data were taken visually by percent control, wherein 0 signifies no herbicidal effect and 100 signifies complete kill.
Herbicidal activity data are shown in Table 4 and Table 5 for the compounds of the above formula(I)
                                  TABLE 4                                 
__________________________________________________________________________
Herbicidal activity for upland test condition (% inhibition)              
__________________________________________________________________________
Compound                                                                  
      Application                                                         
             Test Plant                                                   
No.   method                                                              
          kg/ha                                                           
             ZEAMX                                                        
                  GLXMX                                                   
                       GOSHI                                              
                           TRZAW                                          
                                ORYSA                                     
                                    SORBI                                 
                                        ECHOR                             
__________________________________________________________________________
  1 PRE 1.000 60   0 0 60  100  60  100                                   
    1.250 10  0 0 20  100  20  80                                         
    0.063 0 0 0 0 30  0 30                                                
    0.016 0 0 0 0 0 0 0                                                   
   POST 1.000 100  60  50  100  100  100  100                             
    1.250 100  20  40  60  100  60  100                                   
    0.063 30  0 30  40  50  20  100                                       
    0.016 0 0 0 30  0 0 60                                                
  2 PRE 1.000 100  0 0 80  100  100  100                                  
    1.250 40  0 0 20  60  30  100                                         
    0.063 0 0 0 0 0 0 40                                                  
    0.016 0 0 0 0 0 0 0                                                   
   POST 1.000 100  60  70  100  100  100  100                             
    1.250 100  40  50  100  100  100  100                                 
    0.063 100  30  40  40  40  60  100                                    
    0.016 40  0 0 0 20  0 90                                              
    0.004 0 0 0 0 0 0 80                                                  
  6 PRE 1.000 40  0 0 60  80  30  100                                     
    1.250 0 0 0 20  30  0 50                                              
    0.063 0 0 0 0 30  0 0                                                 
    0.016 0 0 0 0 0 0 0                                                   
   POST 1.000 100  60  50  100  100  70  100                              
    1.250 100  20  40  50  70  50  100                                    
    0.063 60  0 30  30  30  30  100                                       
    0.016 0 0 0 0 0 0 70                                                  
__________________________________________________________________________
Compound                                                                  
      Application                                                         
             Test Plant                                                   
No.   method                                                              
          kg/ha                                                           
             BROJA                                                        
                  DIGSA                                                   
                       PANDI                                              
                            SOLNI                                         
                                 AESIN                                    
                                      ABUTH                               
__________________________________________________________________________
  1 PRE 1.000 100   100  100  0 0 0                                       
    1.250 40  70  100  0 0 0                                              
    0.063 0 30  100  0 0 0                                                
    0.016 0 0 0 0 0 0                                                     
   POST 1.000 100  100  100  0 0 0                                        
    1.250 70  100  100  0 0 0                                             
    0.063 40  100  100  0 0 0                                             
    0.016 0 70  40  0 0 0                                                 
  2 PRE 1.000 100  100  100  0 0 0                                        
    1.250 60  100  100  0 0 0                                             
    0.063 20  60  50  0 0 0                                               
    0.016 0 0 0 0 0 0                                                     
   POST 1.000 100  100  100  0 0 0                                        
    1.250 100  100  100  0 0 0                                            
    0.063 60  100  100  0 0 0                                             
    0.016 0 100  40  0 0 0                                                
    0.004 0 100  0 0 0 0                                                  
  6 PRE 1.000 80  100  100  0 0 0                                         
    1.250 40  60  100  0 0 0                                              
    0.063 0 0 80  0 0 0                                                   
    0.016 0 0 0 0 0 0                                                     
   POST 1.000 100  100  100  30  20  30                                   
    1.250 70  100  100  0 0 0                                             
    0.063 30  100  100  0 0 0                                             
    0.016 0 60  40  0 0 0                                                 
__________________________________________________________________________

                                  TABLE 5                                 
__________________________________________________________________________
Herbicidal activity for paddy test (% inhibition)                         
Compound                                                                  
      Application                                                         
            ORYSA                                                         
                ORYSA                                                     
  No. (kg/ha) (3 Leaf) (seed) ECHOR SCPJU MOOVA SAGPY                     
__________________________________________________________________________
1     0.500 100 100 100 0   0    0                                        
   0.125 90  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 70  95  0 0 0                                                  
   0.002 0 0 95  0 0 0                                                    
  2 0.500 100  100  100  0 0 0                                            
   0.125 60  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 80  100  0 0 0                                                 
   0.002 0 30  60  0 0 0                                                  
  3 0.500 100  100  100  0 0 0                                            
   0.125 10  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 10  100  0 0 0                                                 
   0.002 0 0 0 0 0 0                                                      
  4 0.500 40  100  100  0 0 50                                            
   0.125 10  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 0 100  0 0 0                                                   
   0.002 0 0 0 0 0 0                                                      
  6 0.500 65  100  100  0 0 40                                            
   0.125 20  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 0 60  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  7 0.500 65  100  100  0 0 40                                            
   0.125 20  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 20  95  0 0 0                                                  
   0.002 0 0 95  0 0 0                                                    
  8 0.500 0 100  100  0 0 0                                               
   0.125 0 100  100  0 0 0                                                
   0.031 0 60  100  0 0 0                                                 
   0.008 0 0 40  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  9 0.500 0 100  100  0 0 0                                               
   0.125 0 70  100  0 0 0                                                 
   0.031 0 0 100  0 0 0                                                   
   0.008 0 0 50  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  11  0.500 80  100  100  0 50  0                                         
   0.125 30  100  100  0 30  0                                            
   0.031 0 30  70  0 0 0                                                  
   0.008 0 0 30  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  12  0.500 40  100  100  60  50  30                                      
   0.125 0 100  100  0 0 0                                                
   0.031 0 30  100  0 0 0                                                 
   0.008 0 0 70  0 0 0                                                    
   0.002 0 0 30  0 0 0                                                    
  13  0.500 30  100  100  0 30  30                                        
   0.125 0 100  100  0 0 30                                               
   0.031 0 50  100  0 0 0                                                 
   0.008 0 30  50  0 0 0                                                  
   0.002 0 0 30  0 0 0                                                    
  14  0.500 40  100  100  90  100  30                                     
   0.125 0 40  100  30  30  0                                             
   0.031 0 0 100  0 0 0                                                   
   0.008 0 0 70  0 0 0                                                    
   0.002 0 0 30  0 0 0                                                    
  15  0.500 30  100  100  0 30  0                                         
   0.125 0 40  100  0 0 0                                                 
   0.031 0 0 30  0 0 0                                                    
   0.008 0 0 30  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  16  0.500 30  100  100  0 50  30                                        
   0.125 0 100  100  0 50  0                                              
   0.031 0 30  70  0 30  0                                                
   0.008 0 0 30  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  18  0.500 0 100  100  0 0 0                                             
   0.125 0 30  100  0 0 0                                                 
   0.031 0 0 70  0 0 0                                                    
   0.008 0 0 30  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  19  0.500 0 30  100  0 0 0                                              
   0.125 0 0 100  0 0 0                                                   
   0.031 0 0 80  0 0 0                                                    
   0.008 0 0 50  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  21  0.500 100  100  100  0 70  0                                        
   0.125 80  100  100  0 60  0                                            
   0.031 0 100  100  0 50  0                                              
   0.008 0 100  95  0 30  0                                               
   0.002 0 20  40  0 0 0                                                  
  22  0.500 100  100  100  0 60  0                                        
   0.125 20  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 0 95  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  23  0.500 60  100  100  0 0 0                                           
   0.125 0 100  100  0 0 0                                                
   0.031 0 100  100  0 0 0                                                
   0.008 0 10  40  0 0 0                                                  
   0.002 0 0 0 0 0 0                                                      
  25  0.500 50  100  100  0 0 0                                           
   0.125 0 100  100  0 0 0                                                
   0.031 0 60  100  0 0 0                                                 
   0.008 0 0 0 0 0 0                                                      
   0.002 0 0 0 0 0 0                                                      
  26  0.500 30 100  100  40  0 0                                          
   0.125 0 100  100  0 0 0                                                
   0.031 0 20  100  0 0 0                                                 
   0.008 0 0 0 0 0 0                                                      
   0.002 0 0 0 0 0 0                                                      
  27  0.500 0 100  100  0 0 0                                             
   0.125 0 100  100  0 0 0                                                
   0.031 0 0 50  0 0 0                                                    
   0.008 0 0 0 0 0 0                                                      
   0.002 0 0 0 0 0 0                                                      
  38  0.500 100  100  100  0 0 0                                          
   0.125 50  100  100  0 0 0                                              
   0.031 0 100  100  0 0 0                                                
   0.008 0 20  95  0 0 0                                                  
   0.002 0 0 0 0 0 0                                                      
  39  0.500 80  100  100  0 0 0                                           
   0.125 0 100  100  0 0 0                                                
   0.031 0 100  100  0 0 0                                                
   0.008 0 0 80  0 0 0                                                    
   0.002 0 0 0 0 0 0                                                      
  40  0.500 0 100  100  0 0 0                                             
   0.125 0 0 100  0 0 0                                                   
   0.031 0 0 0 0 0 0                                                      
   0.008 0 0 0 0 0 0                                                      
   0.002 0 0 0 0 0 0                                                      
  42  0.500 0 100  100  0 0 0                                             
   0.125 0 100  100  0 0 0                                                
   0.031 0 20  80  0 0 0                                                  
   0.008 0 0 0 0 0 0                                                      
   0.002 0 0 0 0 0 0                                                      
__________________________________________________________________________
The compounds of formula (I) of the present invention are used as herbicides or plant growth regulants, for example, the above compounds are suitable for selective elimination of weeds when useful plant is cultivated. Also, the compounds of formula (I) have the effect of growth inhibition and growth regulation for useful plant, for example, cereals, soybean, wheat or rice.
The compounds of formula (I) as prominent herbicides, may be applied directly to soil for pre-emergence treatment and to the plant for post-emergence treatment. The compounds of formula (I) of the present invention generally have more prominent herbicidal activity when are treated to leaves for post-emergence, and have strong safety for the broad-leaved plant, for example, soybean, cotton, sulflower, sugarbeet or vegetables. And these compounds have selectively herbicidal activity against grasses, and may be useful as herbicides in broad-leaved crops.
Certain of formula (I) compounds of the present invention especialy have prominent selectivity within the group of grasses and may be used at rate sufficient to control grass weeds in cultivated crops, for example, rice, wheat or barley, and have selectively herbicidal activity against wild grasses such as wildoat or barnyardgrass.

Claims (5)

What is claimed is:
1. A process for the preparation of 2-methyl-2-alkylindanaldehyde of formula (7), which consists of
preparing the 2-methyl-2-alkylindan-1,3-dione of formula (9) by reacting the benzene derivative of formula (8) with a malonyl halide of the formula ##STR13## in the presence of Lewis acid; preparing the 2-methyl-2-alkylindane of formula (10) by reduction of the above compound (9) in the presence of hydrochloric acid and zinc-mercury alloy (Zn/Hg); and
reacting the compound (10) with α,α-dichloromethyl methyl ether in the presence of Lewis acid as catalyst, ##STR14## wherein X is selected from the group consisting of hydrogen, halogen, C1 ˜C8 alkyl, C2 ˜C6 alkoxy, C1 ˜C6 haloalkyl, nitro, C1 ˜C6 alkylthio, C1 ˜C6 alkylsulfinyl, C1 ˜C6 alkylsulfonyl, C1 ˜C6 sulfamoyl, and N,N-di(C1 ˜C6 alkyl) sulfamoyl;
(X)n represents the number of X substituents which may be substituted on the benzene ring, wherein n is 1, 2, or 3; and
R1 is selected from the group consisting of hydrogen and C1 ˜C6 alkyl.
2. A process according to claim 1, wherein X is selected from the group consisting of hydrogen, halogen and C1 ˜C6 alkyl; n is 1, 2, or 3; and R1 is selected from the group consisting of hydrogen and C1 ˜C6 alkyl.
3. A process according to claim 2, wherein X is methyl and n is 3.
4. A process according to claim 2, wherein R1 is selected from the group consisting of methyl and ethyl.
5. A process according to claim 1, wherein R1 is selected from the group consisting of methyl and ethyl.
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US6218579B1 (en) * 1997-11-27 2001-04-17 Zeneca Limited Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds
US6504036B1 (en) * 1996-08-05 2003-01-07 Bayer Aktiengesellschaft 2- and 2.5-substituted phenylketoenols

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Smith et al., `Polyalkylbenzenes, etc.` Journal of the American Chemical Society, 73, 3843-3847, Aug. 1951.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6504036B1 (en) * 1996-08-05 2003-01-07 Bayer Aktiengesellschaft 2- and 2.5-substituted phenylketoenols
US6218579B1 (en) * 1997-11-27 2001-04-17 Zeneca Limited Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds

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